Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/48—Separation; Purification; Stabilisation; Use of additives
  • C07C67/62—Use of additives, e.g. for stabilisation

Definitions

• the present invention relates to a process for inhibition of polymerization of a (meth)acrylate ester.
• both the (meth)acrylic acid as a raw material and the hydroxyalkyl (meth)acrylate as the objective product have so polymerizable an unsaturated group as to easily polymerize due to such as light and heat. Therefore, it is important to inhibit their polymerization.
• General methods therefor involve using polymerization inhibitors, and the use of various polymerization inhibitors is attempted. Known as specific examples thereof are methods that involve using such as N-oxyl compounds and nitroso compounds.
• JP-B-046496/1983 discloses a method that involves using an N-oxyl compound (e.g. 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl and 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl) as a polymerization inhibitor in order to inhibit the polymerization of ⁇ , ⁇ -unsaturated carboxylate esters.
• JP-A-194346/1993 discloses a method that involves using an N-nitroso-N-phenyl-N-hydroxylamine salt as a polymerization inhibitor in order to inhibit the polymerization of unsaturated monomers such as acrylic acid and esters thereof.
• 2725638 proposes a method that involves using, together with the N-oxyl compound, at least one member selected from the group consisting of manganese salt compounds, copper salt compounds, 2,2,6,6-tetramethylpiperidine compounds, and nitroso compounds as polymerization inhibitors in order to inhibit the polymerization of (meth)acrylic acid and esters thereof.
• An object of the present invention is to provide a process for inhibition of polymerization of a (meth)acrylate ester, which has an extremely higher effect of inhibition of polymerization than in cases where conventional polymerization inhibitors are used.
• the present inventors have diligently studied in order to solve the above-mentioned problems. As a result, they have found out that surprisingly, the above problems can be solved by: using an N-oxyl compound and at least one member selected from the group consisting of manganese salt compounds, copper salt compounds, 2,2,6,6-tetramethylpiperidine compounds, and nitroso compounds together as polymerization inhibitors, and further using an acid.
• an N-oxyl compound and at least one member selected from the group consisting of manganese salt compounds, copper salt compounds, 2,2,6,6-tetramethylpiperidine compounds, and nitroso compounds are used together as polymerization inhibitors, and further an acid is used.
• (meth)acrylate ester to which the present invention process for inhibition of polymerization is applicable, yet examples thereof include: acrylate esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and hydroxyalkyl acrylates; and methacrylate esters, such as methyl methacrylate, butyl methacrylate, and hydroxyalkyl methacrylates.
• the addition reaction between (meth)acrylic acid and an alkylene oxide is carried out in the presence of a catalyst.
• the conversion of this addition reaction is frequently less than 100%, and therefore it is general that such as unreacted (meth)acrylic acid and unreacted alkylene oxide remain in the resultant reaction liquid at the end of the reaction. Therefore, after the end of the reaction, the above reaction liquid is led to a step for removing such as these unreacted raw materials from the reaction liquid. Then, as the subsequent final step, the purification is carried out by such as distillation, thus obtaining the objective hydroxyalkyl (meth)acrylate.
• the amount of the alkylene oxide is favorably not smaller than 1 mol, more favorably in the range of 1.0 to 10.0 mols, still more favorably 1.0 to 5.0 mols, yet still more favorably 1.0 to 3.0 mols, particularly favorably 1.0 to 2.0 moles, relative to 1 mol of the (meth)acrylic acid.
• the amount of the alkylene oxide as charged is smaller than 1.0 mol, there are disadvantages in that: the conversion is lowered, and by-products are increased.
• the amount of the alkylene oxide as charged is too large, particularly, larger than 10 mols, there are economical disadvantages in that there is a case where a recovery step is necessary.
• the alkylene oxide is favorably an alkylene oxide having 2 to 6 carbon atoms, more favorably having 2 to 4 carbon atoms.
• examples thereof include ethylene oxide, propylene oxide, and butylene oxide.
• the ethylene oxide and the propylene oxide are favorable.
• reaction between the (meth)acrylic acid and the alkylene oxide in the presence of the catalyst can be carried out according to methods as generally used in this kind of reaction.
• the reaction is carried out by introducing a liquid alkylene oxide into the (meth)acrylic acid.
• the alkylene oxide may be introduced after the unsaturated carboxylic acid has been dissolved into a solvent.
• the alkylene oxide may be added in a lump or continuously or intermittently.
• the reaction is continued still after the introduction of the alkylene oxide, thus carrying out what is called aging to complete the reaction.
• the reaction is carried out by continuously charging the (meth)acrylic acid and a liquid alkylene oxide into such as a tubular or tank-type reactor and continuously extracting the resultant reaction liquid from the reactor.
• the catalyst may be continuously supplied together with the raw materials and continuously extracted together with the reaction liquid.
• the catalyst may be used in what is called a fixed-bed manner such that a solid catalyst is used in the form packed in the reactor.
• the catalyst in the case of such as the tank-type reactor, the catalyst may be used in what is called a fluidized-bed manner such that a solid catalyst is used in the form fluidized together with the reaction liquid in the reactor.
• the raw (meth)acrylic acid and the raw alkylene oxide into the reactor may be added from different addition lines, or they may be added after having beforehand been mixed by using such as piping, a line mixer, or a mixing tank before being added to the reactor.
• these liquids may be added to the reactor after having been mixed with the raw (meth)acrylic acid and the raw alkylene oxide.
• the molar ratio of the (meth)acrylic acid in the reaction liquid is excessive in the neighborhood of an addition inlet of the (meth)acrylic acid, therefore it is favorable that the raw materials may be added after having beforehand been mixed together by using such as piping before being added to the reactor.
• the reaction is usually carried out in the reaction temperature range of favorably 40 to 130° C., more favorably 50 to 100° C.
• the reaction temperature is lower than 40° C.
• the proceeding of the reaction is so slow as to deviate from a practical use level.
• the reaction temperature is higher than 130° C.
• by-products are increased, or there occur such as polymerizations of the (meth)acrylic acid as a raw material and of the hydroxyalkyl (meth)acrylate as the objective product.
• the reaction may be carried out in a solvent.
• a solvent Usable as the solvent are general solvents such as toluene, xylene, heptane, and octane.
• the pressure in the system during the reaction depends upon the kinds and mixing ratios of the raw materials as used, but generally the reaction is carried out under increased pressure.
• the unreacted alkylene oxide and/or the unreacted (meth)acrylic acid may be recovered and reused as the raw reaction materials for the hydroxyalkyl (meth)acrylate.
• the recovered unreacted raw materials may contain the hydroxyalkyl (meth)acrylate.
• the hydroxyalkyl (meth)acrylate may be added to the reactor after having been mixed with the recovered raw materials in view of controlling the heat of the reaction as generated.
• the amount of the hydroxyalkyl (meth)acrylate as added to the reactor increases, the amounts of formed by-products such as diesters increase.
• the amount of the hydroxyalkyl (meth)acrylate as contained in the recovered raw materials is favorably not larger than 4.0 times, more favorably not larger than 2.0 times, still more favorably not larger than 1.0 time, based on the weight relative to the total amount of the recovered raw acid and the raw acid as freshly added.
• catalysts as generally used in this kind of reaction.
• favorably usable is at least one member selected from the group consisting of: chromium compounds, such as chromium chloride, chromium acetylacetonate, chromium formate, chromium acetate, chromium acrylate, chromium methacrylate, sodium bichromate, and chromium dibutyldithiocarbamate; iron compounds, such as iron powders, iron chloride, iron formate, iron acetate, iron acrylate, and iron methacrylate; and amine compounds, such as trialkylamines, cyclic amines (e.g. pyridine), their quaternary salts, and resins having basic functional groups (e.g. tertiary amino groups, quaternary ammonium salts, and
• the catalyst is usually used in an amount of 5 to 50 weight %, favorably 10 to 30 weight %, of the raw (meth)acrylic acid.
• the catalyst is usually used in the range of 30 to 90 vol %, favorably 50 to 80 vol %, of the volume of the reaction liquid.
• a liquid containing the raw reaction materials is favorably passed through the reactor at a liquid space velocity (LHSV: h ⁇ 1 ) of 0.05 to 15, more favorably 0.2 to 8.
• LHSV liquid space velocity
• the catalyst is usually used in amount of 0.05 to 10 weight %, favorably 0 1 to 3 weight %.
• the crude hydroxyalkyl (meth)acrylate as obtained may further be purified when the occasion demands.
• the purification method yet examples thereof include purification by distillation. More particularly, specific examples thereof include distillation by using such as: distillation columns (as widely used) and rectifying columns (e.g. packed columns, bubble-cap columns, perforated-plate columns), but there is no especial limitation thereto.
• other purification means may be used together with the purification by the distillation.
• the purification by the distillation can be carried out under conditions as generally used for the distillation of the hydroxyalkyl (meth)acrylate. Specifically, the distillation is carried out, for example, at a temperature of 50 to 120° C.
• the N-oxyl compound and the at least one member selected from the group consisting of manganese salt compounds, copper salt compounds, 2,2,6,6-tetramethylpiperidine compounds, and nitroso compounds are used together as polymerization inhibitors.
• manganese salt compounds include manganese dialkyldithiocarbamates (wherein the alkyl groups are any ones of a methyl group, an ethyl group, a propyl group, and a butyl group, and may be either identical with or different from each other), manganese diphenyidithiocarbamate, manganese formate, manganese acetate, manganese octanoate, manganese naphthenate, manganese permanganate, and manganese ethylenediaminetetraacetate.
• the manganese salt compounds may be used either alone respectively or in combinations with each other.
• copper salt compounds Although there is no especial limitation on the copper salt compounds, yet examples thereof include copper dialkyldithiocarbamates (wherein the alkyl groups are any ones of a methyl group, an ethyl group, a propyl group, and a butyl group, and may be either identical with or different from each other) and copper diphenyldithiocarbamate.
• the copper salt compounds may be used either alone respectively or in combinations with each other.
• 2,2,6,6-tetramethylpiperidine compounds Although there is no especial limitation on the 2,2,6,6-tetramethylpiperidine compounds, yet examples thereof include 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-2,2,6,6-tetramethylpiperidine, and 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine.
• the 2,2,6,6-tetramethylpiperidine compounds may be used either alone respectively or in combinations with each other.
• nitroso compounds include nitrosophenol, N-nitrosodiphenylamine, isoamyl nitrite, N-nitroso-cyclohexylhydroxylamine, N-nitroso-N-phenylhydroxylamine, and their salts.
• the nitroso compounds may be used either alone respectively or in combinations with each other.
• N-oxyl compound yet examples thereof include 2,2,4,4-tetramethylazetidine-1-oxyl, 2,2-dimethyl-4,4-dipropylazetidine-1-oxyl, 2,2,5,5-tetramethylpyrrolidine-1-oxyl, 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 6-aza-7,7-dimethyl-spiro(4,5)decane-6-oxyl, 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-benzoyloxypiperidine-1-oxyl, and 4,4′,4′′-tris-(2,2,6,6-tetramethylpiperidine-1-oxyl) phosphite.
• the N-oxyl compounds may be used either alone respectively or
• the N-oxyl compound and the at least one member selected from the group consisting of the manganese salt compounds, the copper salt compounds, the 2,2,6,6-tetramethylpiperidine compounds, and the nitroso compounds are used together as the polymerization inhibitors, but other polymerization inhibitors may be used together with these polymerization inhibitors when the occasion demands. There is no especial limitation on such other polymerization inhibitors, and usable are publicly known polymerization inhibitors as generally used.
• phenol compounds such as hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,4-dimethyl-6-tert-butylphenol, hydroquinone monomethyl ether, cresol, and tert-butylcatechol;
• p-phenylenediamines such as N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, and N,N′-di-2-naphthyl-p-phenylenediamine; amines, such as
• the amount of the polymerization inhibitors as used is fitly adjusted according to such as operational conditions, and it is not especially limited. However, the total amount of the polymerization inhibitors as used is favorably in the range of 0.00001 to 1 weight %, more favorably 0.00005 to 0.1 weight %, still more favorably 0.0001 to 0.05 weight %, of the (meth)acrylate ester. As to the amounts of the individual polymerization inhibitors as used, the N-oxyl compound is used in an amount of favorably 0.00001 to 0.5 weight %, more favorably 0.00005 to 0.1 weight %, still more favorably 0.0001 to 0.05 weight %, of the (meth)acrylate ester.
• the manganese salt compound is used in an amount of favorably 0.00001 to 0.5 weight %, more favorably 0.00005 to 0.1 weight %, still more favorably 0.0001 to 0.05 weight %, of the (meth)acrylate ester.
• the copper salt compound is used in an amount of favorably 0.00001 to 0.5 weight %, more favorably 0.00005 to 0.1 weight %, still more favorably 0.0001 to 0.05 weight %, of the (meth)acrylate ester.
• the 2,2,6,6-tetramethylpiperidine compound is used in an amount of favorably 0.00001 to 0.5 weight %, more favorably 0.00005 to 0.1 weight %, still more favorably 0.0001 to 0.05 weight %, of the (meth)acrylate ester.
• the nitroso compound is used in an amount of favorably 0.00001 to 0.5 weight %, more favorably 0.00005 to 0.1 weight %, still more favorably 0.0001 to 0.05 weight %, of the (meth)acrylate ester.
• amount of the polymerization inhibitors as used is smaller than the above range, it tends to be impossible to sufficiently obtain the effect of inhibition of polymerization.
• amount is larger than the above range, there are disadvantages of being uneconomical.
• the polymerization inhibitors are added in such a manner that the polymerization of the (meth)acrylate ester can be inhibited, the polymerization inhibitors can be added, in any mode and by any method, to any place of all the steps of the production process for the (meth)acrylate ester.
• the polymerization inhibitors may be added in such a manner that the polymerization inhibitors can coexist with the (meth)acrylic eater in any step in which the polymerization tends to occur, favorably in such as a reaction step, an aging step, and a distillation step, more favorably in such as a distillation step, still more favorably in a distillation step after the residual unreacted alkylene oxide has been removed, yet still more favorably in a distillation step after the residual unreacted (meth)acrylic acid and alkylene oxide have been removed.
• carboxylic acids and carboxylic anhydrides such as oxalic acid, oxalic anhydride, malonic acid, succinic acid, succinic anhydride, fumaric acid, maleic acid, maleic anhydride, octanoic acid, adipic acid, sebacic acid, tetradecanedicarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 1,6,7,12-dodecanetetracarboxylic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicar
• the acid may be added in a lump, but the acid is favorably added one by one in the form divided into at least two portions.
• the acid When the acid is added in a lump in the reaction step, there is a possibility that the acid may be consumed, for example, by partially or entirely reacting with the alkylene oxide. Also, this acid has the effect of suppressing the formation of diesters, and therefore there is a possibility that this effect may be lost (deactivated) by the consumption of the acid. Accordingly, for preventing or suppressing the formation of diesters in the reaction step by adding the acid, it is necessary to add a large amount of the acid in consideration of a deactivated portion of the acid.
• the acid When the acid is added one by one in the form divided into at least two portions, there is no especial limitation on the number of the divided portions. However, the acid is favorably added one by one in the form divided into 2 to 10 portions, particularly favorably 3 portions, in consideration of such as workability.
• the method (9) is favorably used.
• the method for the divided additions of the acid is not limited to the above methods (1) to (10).
• the acid can be added to any place of all the steps of the production process for the (meth)acrylate ester.
• the total amount of the acid as added is favorably in the range of 0.0001 to 1 weight %, more favorably 0.001 to 1 weight %, still more favorably 0.005 to 0.5 weight %, relative to the (meth)acrylate ester.
• the total amount of the acid as added is smaller than 0.0001 weight % relative to the (meth)acrylate ester, there are disadvantages in that: it tends to be impossible to sufficiently obtain the effect of inhibition of polymerization, and also it tends to be impossible to effectively suppress the formation of diesters.
• the total amount of the acid as added is larger than 1 weight %, there are disadvantages in that there is a tendency to easily cause the deterioration of the behavior and state of the distillation bottom liquid in the distillation step.
• the amount of the acid as added to each place to which the addition is to be made should be determined in such a range that at least the effect of the acid can be obtained.
• This range depends upon the kind of the acid, and therefore it cannot be specified sweepingly.
• the amount is usually in the range of favorably 0.0001 to 1 weight %, more favorably 0.001 to 1 weight %, still more favorably 0.005 to 0.5 weight %, relative to the (meth)acrylate ester.
• the acid is added either after the alkylene oxide concentration in the reaction liquid has decreased to favorably not larger than 10 weight %, more favorably not larger than 5 weight %, still more favorably not larger than 3 weight %, with the passage of the reaction or after the alkylene oxide concentration in the reaction liquid has been adjusted to favorably not larger than 10 weight, more favorably not larger than 5 weight %, still more favorably not larger than 3 weight %, by adding a solvent inactive to the reaction (e.g.
• the acid is added to the starting raw material before the beginning of the reaction, and thereafter the reaction is carried out while the alkylene oxide concentration in the reaction liquid is maintained in the range of favorably not larger than 10 weight %, more favorably 0.1 to 10 weight %, more favorably 0.1 to 5 weight %.
• the liquid alkylene oxide may be introduced into the starting raw material little by little continuously or intermittently.
• the reaction is carried out while the alkylene oxide concentration in the reaction liquid is maintained in the range of not larger than 10 weight % in the aforementioned methods (1) to (3) and (7) to (9) (particularly in the methods (7) to (9)).
• a still-higher-quality hydroxyalkyl ester having a still lower diester content can be obtained by distilling the reaction product as obtained in the above way.
• the deterioration of the behavior and state of the distillation bottom liquid during the distillation can also be prevented effectively, because the total amount of the acid as used can be decreased.
• the present invention process can sufficiently prevent the polymerizations of the (meth)acrylic acid as a raw material and of the (meth)acrylate ester as the objective product, and further can sufficiently suppress the formation of diesters.
• the present invention is more specifically illustrated by the following examples of some preferred embodiments in comparison with comparative examples not according to the invention.
• the present invention is not limited to the following examples.
• the hydroxyethyl acrylate as used in the examples was that from which the stabilizer had been removed by purification.
• a glass-made container was charged with 100 g of hydroxyethyl acrylate, and then thereto 0.002 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (0.002 weight %), 0.002 g of manganese acetate (0.002 weight %), and 0.1 g of maleic acid (0.1 weight %) were further added. Subsequently, the pressure in the glass-made container was reduced to 4 hPa, and immediately thereafter the glass-made container was immersed into an oil bath as adjusted to 80° C., and how long time passed until a polymerized product formed was checked with the eye. As a result, after 2.5 hours had passed, the polymerized product began to form. The result is listed in Table 1.
• Example 2 The same procedures as of Example 1 were carried out except that the polymerization inhibitors as listed in Table 1 or Table 2 were used instead of the 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, the manganese acetate, and the maleic acid as the polymerization inhibitors. The results are listed in Table 1 or Table 2.
• Example 2 The same procedures as of Example 1 were carried out except that the polymerization inhibitors as listed in Table 3 or Table 4 were used instead of the 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, the manganese acetate, and the maleic acid as the polymerization inhibitors. The results are listed in Table 3 or Table 4.
• Example 1 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.002 2.5 Manganese acetate 0.002 Maleic acid 0.1
• Example 2 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.002 2.0 Copper dibutyldithiocarbamate 0.002 Maleic acid 0.1
• Example 3 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.002 2.0 4-Hydroxy-2,2,6,6-tetramethylpiperidine 0.002 Maleic acid 0.1
• Example 4 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.002 2.5 N-Nitroso-N-phenylhydroxylamine ammonium salt 0.002 Maleic acid 0.1
• Example 5 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl
• Example 8 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.001 2.0 Manganese acetate 0.001 Copper dibutyldithiocarbamate 0.001 Maleic acid 0.1
• Example 9 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.001 2.0 Manganese acetate 0.001 4-Hydroxy-2,2,6,6-tetramethylpiperidine 0.001 Maleic acid 0.1
• Example 10 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.001 2.0 Manganese acetate 0.001 N-Nitroso-N-phenylhydroxylamine ammnonium salt 0.001 Maleic acid 0.1
• Example 11 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.001 1.8 Copper dibutyldithio

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polymerisation Methods In General (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=27764495

Family Applications (1)

Country Status (6)

Cited By (3)

Families Citing this family (7)

Citations (8)

• 2002
  • 2002-03-12 JP JP2002067544A patent/JP3990580B2/ja not_active Expired - Lifetime
• 2003
  • 2003-02-11 US US10/361,973 patent/US7241915B2/en active Active
  • 2003-02-12 EP EP03003059A patent/EP1344764B1/en not_active Expired - Lifetime
  • 2003-02-12 TW TW092102901A patent/TWI255819B/zh not_active IP Right Cessation
  • 2003-03-05 KR KR1020030013589A patent/KR100592437B1/ko active IP Right Grant
  • 2003-03-12 CN CNB031200745A patent/CN1228306C/zh not_active Expired - Lifetime

Patent Citations (13)

Also Published As

Similar Documents

Legal Events